Dyestuffs of the anthraquinone series and process of making same



Patented May 3, 1932 UNITED FFICE OSCAR BALLY, PAUL GROSSMANN, AND FRIEDRICH FELIX, OF BASEIJ, SWITZERLAND,

ASSIGNORS TO THE FIRM OF SOCIETY OF CHEMICAL INDUSTRY IN BASLE; 0F BASEL,

SWITZERLAND DYESTUFIES 01? THE ANTHRAQUINONE SERIES AND PROCESS OF MAKING SAME No Drawing. Application filed January 27, 1928, Serial No. 250,080, and in Switzerland February 12, 1927.

wherein m stands for OH, OCH or NI-L, to interact with aromatic diamine compounds, such as phenylenediamine, naphthylenediamine, benzidine or the like, or a derivative, homologue or substitution product thereof. There areproduced l-arylidol-aminoanthraquinones, which contain in the aryl-nucleus I O NHa at least one amino-group or a group derived from the amino-group.

By treating these new l-arylido--aminoa-nthraquinones by an agent capable of introducing a sulphonic acid group, such as a sulphonating agentor an aldehyde bisulfite,

they may be converted into new sulphonic acids. The new products correspond with the general formula 7 the aryl groupings may or may not contain sulfo groups. They are dark powders which dissolve in sulfuric acid with violet to blue and green-blue colorations, and in water or organic solvents to blue to greenish-blue solutions, dyeing wool or cellulose esters and ethers, such as acetate silk or varnishes or lacquers, similar tints.

The following examples illustrate the invention, the parts being by weight Example 1 25 parts of l-methoxy-l-amino-anthraquinone are heated with parts of para-phenylenediamine and 100 parts of dimethylaniline at 180 C. until a sample in alcohol shows no further change of tint. Then 140 parts of methyl alcohol are added at 100 C. and the product is filtered after it has cooled. The 1- (F-amino) -phenylamino-4- amino-anthraquinone separates in good yield and pure form. It is filtered and dried. It melts at 24:724E8 (3.; dissolves in organic solvents to a greenish blue solution and in concentrated sulphuric acid to a violet solution and dyes acetate silk greenish blue tints. The formula of the new product is g NH:

Instead of dimethylaniline, nitrobenzene, orthodichlorbenzene, naphthalene or another solvent may be used. So also for the para-phenylenediamine, theorthoor metacompound may be substituted, whereby pure blue acetate silk dyestuffs are obtained; or dimethyl para phenylenediamine, metatoluylenediamine, acetyl-para-phenylenediamine, benzidine, 5-amino-2-methylbenzimidazolor the like may be used. The formulas EN 0 H H 1 I O N O of some of these new compounds thus obtained are All these compounds dissolve in concentrated sulfuric acid with violet to blue coloration.

'Emample 2 24 parts of 'il-hydroxy--aminoanthraquinone are heatedtogetherwith 12parts o'fboric acid,43 parts ofpara-phenylenediamine and lOO part-s of dimethylaniline at 150C. until a sample-in alcohol-no longershows an appreciable shifting of the colour towards'blue. The dimethylaniline is then distilled with steam, the residue filtered and the solid matter dried and crystallized from sulphuric acid or aniline, whereby the same product is obtained as is describe'din Example 1.

:5 ,;parts zO f 1-(4-amino)-ephenylamino-taminoanthraquinone are heated in parts of oleum of 7;.per cent; strength v at 50- C. until a sample is completely solublein dilute ammonia solution. The mass is then poured intoice-water,commonsalt is added and the whole filtered, the.-solidmatter being washed :with salt solution'until neutral. This prod- -uct dissolves inwater to .a greeni'sh1blue solu- --tion in concentrated" sulfuric acidto a .violet solution. 'It' dyesnonrmordanted woolin an acid bathfast, .pu-reggreenish blue tints. The

position .where the sulfo group :enters the molecule is not known.

'Ewample 4 wherein m stands for Example 5 5 parts of 1- (4.'-a1nino) -phenylamino-4- aminoanthraquinone are brought into a fine state of subdivision by dissolution in sulfuric acid and pouring the solution into water, and in this condition the amino-derivative is stirred for a long time at 80 C. with an excess of formaldehyde bisulfite solution. The mass -etc.

is then diluted with hot water, separated from some undissolved matter and the dyestuff is salted outfromr the filtrate. ilhe newsulfonic acid dissolves in water and in sulfuric acid -with green-blue coloration; it dyes wool uniform, fastblue-green tints.

Emample 6 15 :parts of 1- (AU-amino)-phenylaminolaminoanthraquinone are stirredwith :sulfite cellulose lye or a sulfonation product ofthe distillation= residue obtained in the manufacture of benzaldehyde or turpentine to produce a uniform paste of 20 per cent. strength.

5 parts of this paste. are stirred with about the same quantity of soap solution of 6 per cent. strength at about C. and then diluted with lukewarm waterso as to form 300 parts.

10 parts of acetate silk are then entered, the

temperature is raised within hour to 7 580 C. and the silk is handled for about -hour at this temperature. "Washing and drying-follow. The acetate silk is dyed a beautiful green-blue, which isfast.

What we claim is v 1. Amanufacture of new dyestuffs by causing a product of the generalformula interact at araised temperature with anarcmatic diamine compound in which at least'one of the amino-groups is present as an unsubstituted NIL-group. V

2. A manufacture'of'new dyestuffs by causing a product of the general formula O a: *II I I l i O NHz wherein m stands for OH, OGH or"NH ,'to

interact iat'il raised temperature with an aromatic diamine compound in which at least one of the amino-groups ispresent as an unsubstituted. NH -group, and by treating the products thus obtained with agents which are adapted to introduce sulfonic acid groups.

3. .A manufacture of new dyestufis by causing a product of the general formula (I) NH:

wherein it stands for OH, 001-1 or NH to interact at a raised temperature with an aromatic diamine compound of the benzene series in which at least one of the amino-groups is present as an unsubstituted NH -group.

4. A manufacture of new dyestuffs by causing a product of the general formula O a: II

N O NH2 wherein m stands for OH, OCH, or NH to interact at a raised temperature with a pphenylenediamine compound in which at least one of the amino-groups is present as an unsubstituted NH -group.

5. A manufacture of new dyestufis by causing a product of the general formula O a: ll

wherein it stands for OH, OCH or NH to interact at a raised temperature with pphenylenediamine.

6. As new products the l-arylido-l-aminoanthraquinones which contain in the arylnucleus at least one amino-group, which prolducts correspond with the general formu a O NHa wherein the positions 2, 3, 5, 6, 7 and 8 are occupied by hydrogen atoms R- and R signifying hydrogen, alkyl or acidyl and wherein the .anthraquinone and the aryl groupings may or may not contain sulfo-groups, and which products dissolve in sulfuric acid with violet to blue and green-blue colorations, in Water or organic solvents to blue to grenish-blue solutions, dyeing wool or cellulose esters and ethers, such as acetate silk or varnishes or lacquers, similar tints.

7 As new products the l-arylido-d-aminoanthraquinones which contain in the arylnucleus at least one amino-group, which products correspond with the general formula ucts correspond with the general formula r 0 NHz wherein the positions2, 3, 5, 6, 7 and 8 are occupied by hydrogenatoms and R and R signify hydrogen, alkyl or acidyl, dissolving in sulfuric acid with violet colorations, in orgranic solvents to blue to greenish-blue solutions, and dyeing cellulose esters and ethers, such as acetate silk or varnishes or lacquers, similar tints.

9. As new products the l-ar'ylido-t-aminoanthraquinones which contain in the arylnucleus at least one amino-group, which products correspond with the general formula:

wherein the positions 2, 3, 6, 7 and 8 are occupied by hydrogen atoms and R and R signify hydrogen, alkyl or acidyl, dissolving in sulfuric acid with violet colorations, in organic solvents to blue to greenish-blue solutions, and dyeing cellulose esters and ethers, such as acetate silk or varnishes or lacquers, similar tints.

10. As a new product the 1arylido-4- aminoanthraquinone which contains in the was i aryl+n=ucleus at least one :amino-group,awhich product corresponds withithe formula O NH2 NHz wherein the anthraquinone and aryl nuclei may contain sulphogroups.

12. As new products, the l-arylido-laminoanthraquinones which contain in the aryl nucleus at least one amino-group, which products correspond with'the formula:

As a new product the .l-arylido-Ataminoanthraquinone the sodium salt vof which corresponds to the formula:

'SOaNa A l THr and dissolves in water to a greenish-blue solution, and in concentratedsulfuric acid to a violet solution, dyeinginonmordanted wool in an acid bath fast, pure greenish-blue tints.

14. As a new product the l-arylidolr --amino-anthraquinone the sodium salt of whichcorresponds to the formula:

SOaNa J and dissolved in water to agreenish-blue solu- -t1on, 1and in concentrated sulfuric acid to a violet-solution, dyeing nonmordante'd wool in 'an acid bath fast, pure'greenish blue tints.

iIn witness whereof we have hereunto signed our namesthisll'tithday of January,

OSCAR BALLY. PAUL .GROSSMANN. 'FRIEDRIGH FELIX. 

